Asymmetric formales and acetales as adjuvants for crop protection

ABSTRACT

The present invention relates to an agrochemical composition comprising a pesticide and an alkoxylate of the formula (I)R1-[AO]n—O—C(R3)(R4)—O—[CH2—CH2—O]m—R2  (I)where R1 is a C6-C32 aliphatic hydrocarbon group, R2 is a C1-C18 aliphatic hydrocarbon group, R3 and R4 are independently from another H or C1-C12 aliphatic hydrocarbon groups, AO is C2-C6 alkyleneoxy group, n is from 1 to 100, and m is from 0 to 10. The invention further relates to the alkoxylate. The invention further relates to a method of preparing the composition by bringing the alkoxylate and the pesticide into contact. Finally, the invention relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants.

This application is a National Stage application of InternationalApplication No. PCT/EP2015/050946, filed Jan. 20, 2015. This applicationalso claims priority under 35 U.S.C. § 119 to European PatentApplication No. 14153297.8, filed Jan. 30, 2014; European PatentApplication No. 14175595.9, filed Jul. 3, 2014; and European PatentApplication No. 14180223.1, filed Aug. 7, 2014.

The present invention relates to an agrochemical composition comprisinga pesticide and an alkoxylate of the formula (I) as defined below. Theinvention further relates to said alkoxylate. The invention furtherrelates to a method of preparing said composition by bringing thealkoxylate and the pesticide into contact. Finally, the inventionrelates to a method of controlling phytopathogenic fungi and/orundesired plant growth and/or undesired insect or mite attack and/or forregulating the growth of plants, wherein said composition is allowed toact on the respective pests, their environment or the crop plants to beprotected from the respective pest, on the soil and/or on undesiredplants and/or on the crop plants and/or on their environment; and toseed containing said composition. The preferred embodiments of theinvention mentioned herein below have to be understood as beingpreferred either independently from each other or in combination withone another.

Adjuvants are important agroformulation auxiliaries and assist inimproving the stability of the formulation and the efficacy of thepesticide. It is an ongoing challenge to identify new adjuvants withimproved properties.

Object of the present invention was to overcome the problems of thestate of the art. The object was solved by an agrochemical compositioncomprising a pesticide and an alkoxylate of the formula (I)R¹—[AO]_(n)—O—C(R³)(R⁴)—O—[CH₂—CH₂—O]_(m)—R²  (I)whereR¹ is a C₆-C₃₂ aliphatic hydrocarbon group,R² is a C₁-C₁₈ aliphatic hydrocarbon group,R³ and R⁴ are independently form another H or C₁-C₁₂ aliphatichydrocarbon groups,AO is C₂-C₆ alkyleneoxy group,n is from 1 to 100, andm is from 0 to 10.

In another form the object was solved an alkoxylate of the formula (I)as defined above, where R¹ is a saturated and branched C₁₃ alkyl, or amixture thereof; or by an alkoxylate of the formula (I) as definedabove, where R¹ is 2-propylheptanol.

The term agrochemical composition refers usually to a composition whichis suitable for a industrial application in controlling phytopathogenicfungi and/or undesired plant growth and/or undesired insect or miteattack and/or for regulating the growth of plants, wherein thecomposition is allowed to act on the respective pests, their environmentor the crop plants to be protected from the respective pest, on the soiland/or on undesired plants and/or on the crop plants and/or on theirenvironment. Industrial application of agrochemical compositions areusually subject to various specific legal restrictions and specificregistration processes. An expert is well aware that other composition,such as cleansing liquors or washing agents, are usually not suitablefor an industrial application in controlling phytopathogenic fungiand/or undesired plant growth and/or undesired insect or mite attackand/or for regulating the growth of plants, wherein the composition isallowed to act on the respective pests, their environment or the cropplants to be protected from the respective pest, on the soil and/or onundesired plants and/or on the crop plants and/or on their environment.

R¹ is usually a monovalent C₆-C₃₂ aliphatic hydrocarbon group or amixture thereof, preferably a C₈-C₂₀ aliphatic hydrocarbon group or amixture thereof. More preferably, R¹ is a linear or branched, saturatedor unsaturated C₈-C₂₀ alkyl (preferably C₁₀-C₂₀ alkyl and in particularC₁₂-C₁₈ alkyl), or a mixture thereof.

Typical examples for R¹ are linear or branched decyl, undecyl, dodecyl,tridecyl, hexadecyl, heptadecyl and octadecyl, or mixture of theaforementioned residues. In another form typical examples for R¹ arelinear or branched decyl, dodecyl, tridecyl, hexadecyl, heptadecyl andoctadecyl, or mixture of the aforementioned residues.

In another preferred form, R¹ is a saturated and branched C₁₃ alkyl, ormixtures thereof.

In another preferred form, R¹ is a saturated and branched decyl ormixtures thereof, in particular 2-propylheptyl.

R² is usually a monovalent C₁-C₁₈ aliphatic hydrocarbon group or amixture thereof, preferably a C₁-C₈ aliphatic hydrocarbon group or amixture thereof. More preferably, R² is a linear or branched, saturatedor unsaturated C₁-C₈ alkyl (preferably C₁-C₆ alkyl and in particularC₂-C₄ alkyl), or a mixture thereof. In another form R² is selected frommethyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, n-hexyl,iso-hexyl, n-octyl, iso-octyl. In a preferred form R² is n-butyl.

R³ and R⁴ are usually independently form another H or monovalent, linearor branched, saturated or unsaturated C₁-C₁₂ (preferably C₁-C₆, inparticular C₁-C₄) aliphatic hydrocarbon groups. In a preferred form R³and R⁴ are independently form another H, methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, n-hexyl, iso-hexyl, n-octyl, iso-octyl.In another preferred form R³ and R⁴ are independently form another H,methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl. In anotherpreferred form R³ and R⁴ are independently form another H or methyl. Inparticular R³ and R⁴ are H.

AO is usually a saturated or unsaturated, linear or branched C₂-C₆alkyleneoxy group. Mixtures of different C₂-C₆ alkyleneoxy group arealso possible (e.g. AO is a mixture of ethyleneoxy and a C₃-C₆alkyleneoxy group, wherein a mixture of ethyleneoxy and propyleneoxy ispreferred). Examples for AO are ethyleneoxy, propyleneoxy, butyleneoxy,or mixtures thereof. AO is more preferably ethylenoxy, or a mixture ofethyleneoxy and propyleneoxy. In particular, AO is ethyleneoxy.

The unit AO is typically bound to the unit R¹ via an oxygen atom of thealkyleneoxy group, such as exemplified by the alkoxylate of formula (II)below.

The index n is usually any value from 1 to 100, preferably from 1, 5 to80, more preferably from 2 to 80, and in particular from 2 to 15. Inanother form n is from 1.5 to 30, preferably from 2 to 15, and inparticular 3 to 10.

The index m is usually any value from 0 to 10, preferably from 0 to 5,more preferably from 1 to 3, and in particular from 1 to 2. In anotherform the index m is one.

The ratio of n to m is usually from 50/1 to 1/1, preferably from 30/1 to1/1, more preferably from 15/1 to 1.5/1, and in particular from 9/1 to2/1.

In another form the alkoxylate is of the formula (I) where R¹ is alinear or branched, saturated or unsaturated C₈-C₂₀ alkyl, R² is C₁-C₆alkyl, R³ and R⁴ are H or C₁-C₄ alkyl, AO is ethyleneoxy, or ethyleneoxyand propyleneoxy, n is from 2 to 80, and m is from 1 to 3.

In another form the alkoxylate is of the formula (I) where R¹ is alinear or branched, saturated or unsaturated C₈-C₂₀ alkyl, R² isn-butyl, R³ and R⁴ are H, AO is ethyleneoxy, n is from 2 to 80, and m isfrom 1 to 3.

In another form the alkoxylate is of the formula (I) where R¹ is alinear or branched, saturated or unsaturated C₁₀-C₂₀ alkyl, R² isn-butyl, R³ and R⁴ are H, AO is ethyleneoxy, n is from 2 to 12, and m isfrom 1 to 2.

In a preferred form the alkoxylate is of formula (I), where AO isethyleneoxy and R³ and R⁴ are H. This form corresponds to the alkoxylateof formula (II)R¹[O—CH₂—CH₂]_(n)—O—CH₂—O—[CH₂—CH₂—O]_(m)—R²  (II),where R¹, R², n and m have the meanings and preferred forms as definedabove.

The alkoxylates of the formula (I) and (II) may be prepared by knownmethods, such as described in EP2267110 (e.g. Examples 3 and 4) orEP0039859. In a first step a symmetric formal or acetal may be preparedfrom alcohol and aldehyde or ketone. In a second step the product theresulting symmetric acetal is reacted with an alkoxylated alcohol toyield the asymmetric acetal. The term “acetal” may refer to a formalwhen formaldehyde is starting material, to a acetal when an aldehyde isstarting material, or to a ketal when an ketone is starting material.

The composition may contain at least 0.1 wt %, preferably at least 1 wt% of the alkoxylate of formula (I). The composition according to theinvention may be present as an agrochemical composition type andcomprises from 1 to 80% by weight of the alkoxylate of formula (I),preferably from 2 to 50% by weight and in particular from 5 to 30% byweight.

The term pesticide refers to at least one active substance selected fromthe group of the fungicides, insecticides, nematicides, herbicides,safeners, biopesticides and/or growth regulators.

Preferred pesticides are fungicides, insecticides, herbicides and growthregulators. Especially preferred pesticides are fungicides. Mixtures ofpesticides of two or more of the abovementioned classes may also beused. The skilled worker is familiar with such pesticides, which can befound, for example, in the Pesticide Manual, 16th Ed. (2013), TheBritish Crop Protection Council, London. Suitable insecticides areinsecticides from the class of the carbamates, organophosphates,organochlorine insecticides, phenylpyrazoles, pyrethroids,neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormoneanalogs, alkyl halides, organotin compounds nereistoxin analogs,benzoylureas, diacylhydrazines, METI acarizides, and insecticides suchas chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox,etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC,buprofezine, cyromazine, amitraz, hydramethylnon, acequinocyl,fluacrypyrim, rotenone, or their derivatives. Suitable fungicides arefungicides from the classes of dinitroanilines, allylamines,anilinopyrimidines, antibiotics, aromatic hydrocarbons,benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones,benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates,carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamideoximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides,dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates,dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides,guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles,imidazolinones, inorganic substances, isobenzofuranones,methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates,oxazolidinediones, oximinoacetates, oximinoacetamides,peptidylpyrimidine nucleosides, phenylacetamides, phenylamides,phenylpyrroles, phenylureas, phosphonates, phosphorothiolates,phthalamic acids, phthalimides, piperazines, piperidines, propionamides,pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines,pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones,quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles,thiazolecarboxamides, thiocarbamates, thiophanates,thiophenecarboxamides, toluamides, triphenyltin compounds, triazines,triazoles. Suitable herbicides are herbicides from the classes of theacetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran,benzoic acids, benzothiadiazinones, bipyridylium, carbamates,chloroacetamides, chlorocarboxylic acids, cyclohexanediones,dinitroanilines, dinitrophenol, diphenyl ether, glycines,imidazolinones, isoxazoles, isoxazolidinones, nitriles,N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides,phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles,phenylpyrazolines, phenylpyridazines, phosphinic acids,phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles,pyridazinones, pyridines, pyridinecarboxylic acids,pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates,quinolinecarboxylic acids, semicarbazones,sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones,thiadiazoles, thiocarbamates, triazines, triazinones, triazoles,triazolinones, triazolocarboxamides, triazolopyrimidines, triketones,uracils, ureas.

Preferably, the pesticide is soluble in water up to 10 g/l, preferablyup to 1 g/l, and in particular up to 0.5 g/l, at 20° C.

The composition according to the invention may also be present in formof an agrochemical formulation comprising the pesticide, the alkoxylateof the formula (I), and optionally an auxiliary. An agrochemicalformulation comprises usually a pesticidally effective amount of apesticide. The term “effective amount” denotes an amount of thecomposition or of the compounds I, which is sufficient for controllingharmful pests on or around cultivated plants or in the protection ofmaterials and which does not result in a substantial damage to thetreated plants. Such an amount can vary in a broad range and isdependent on various factors, such as the fungal species to becontrolled, the treated cultivated plant or material, the climaticconditions and the specific pesticide used.

Suitable, customary types of agrochemical compositions are e. g.solutions, emulsions, suspensions, dusts, powders, pastes, granules,pressings, capsules, and mixtures thereof. Examples for formulationtypes are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g.EC), dispersible concentrates (DC), emulsions (e.g. EW, EO, ES, ME),capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts(e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g.WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gelformulations for the treatment of plant propagation materials such asseeds (e.g. GF). These and further formulation types are defined in the“Catalogue of pesticide formulation types and international codingsystem”, Technical Monograph No. 2, 6^(th) Ed. May 2008, CropLifeInternational.

The agrochemical formulations are often prepared in a known manner, suchas described by Mollet and Grubemann, Formulation technology, Wiley VCH,Weinheim, 2001; or Knowles, New developments in crop protection productformulation, Agrow Reports DS243, T&F Informa, London, 2005.

Examples for suitable auxiliaries are solvents, liquid carriers, solidcarriers or fillers, surfactants, dispersants, emulsifiers, wetters,further adjuvants, solubilizers, penetration enhancers, protectivecolloids, adhesion agents, thickeners, humectants, repellents,attractants, feeding stimulants, compatibilizers, bactericides,anti-freezing agents, anti-foaming agents, colorants, tackifiers andbinders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin; aliphatic,cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones,e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acidesters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides,e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixturesthereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharide powders, e.g. cellulose, starch;fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas; products of vegetable origin, e.g. cereal meal, treebark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures thereof. Such surfactants can be used asemusifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulfonates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulfonates are alkylarylsulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxylates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylate surfactants, N-substitutedfatty acid amides, amine oxides, esters, sugar-based surfactants,polymeric surfactants, and mixtures thereof. Examples of alkoxylatesurfactants are compounds such as alcohols, alkylphenols, amines,amides, arylphenols, fatty acids or fatty acid esters which have beenalkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propyleneoxide may be employed for the alkoxylation, preferably ethylene oxide.Examples of N-substituted fatty acid amides are fatty acid glucamides orfatty acid alkanolamides. Examples of esters are fatty acid esters,glycerol esters or monoglycerides. Examples of sugar-based surfactantsare sorbitans, ethoxylated sorbitans, sucrose and glucose esters oralkylpolyglucosides. Examples of polymeric surfactants are home- orcopolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary ammonium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of polyethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,polyethylene oxide and polypropylene oxide. Suitable polyelectrolytesare polyacids or polybases. Examples of polyacids are alkali salts ofpolyacrylic acid or polyacid comb polymers. Examples of polybases arepolyvinylamines or polyethyleneamines.

Suitable further adjuvants are compounds, which have a neglectable oreven no pesticidal activity themselves, and which improve the biologicalperformance of the pesticide on the target. Examples are surfactants,mineral or vegetable oils, and other auxiliaries. Further examples arelisted by Knowles, Adjuvants and additives, Agrow Reports DS256, T&FInforma UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellulose), anorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, andsalts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of lowwater solubility and water-soluble dyes. Examples are inorganiccolorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) andorganic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

Examples for formulation types and their preparation are:

i) Water-Soluble Concentrates (SL, LS)

10-60 wt % of the pesticide and 5-15 wt % wetting agent (e.g. alcoholalkoxylates) are dissolved in water and/or in a water-soluble solvent(e.g. alcohols) up to 100 wt %. The active substance dissolves upondilution with water.

ii) Dispersible Concentrates (DC)

5-25 wt % of the pesticide and 1-10 wt % dispersant (e. g.polyvinylpyrrolidone) are dissolved in up to 100 wt % organic solvent(e.g. cyclohexanone). Dilution with water gives a dispersion.

iii) Emulsifiable Concentrates (EC)

15-70 wt % of the pesticide and 5-10 wt % emulsifiers (e.g. calciumdodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in upto 100 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon).Dilution with water gives an emulsion.

iv) Emulsions (EW, EO, ES)

5-40 wt % of the pesticide and 1-10 wt % emulsifiers (e.g. calciumdodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon).This mixture is introduced into up to 100 wt % water by means of anemulsifying machine and made into a homogeneous emulsion. Dilution withwater gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % of the pesticide are comminutedwith addition of 2-10 wt % dispersants and wetting agents (e.g. sodiumlignosulfonate and alcohol ethoxylate), 0.1-2 wt % thickener (e.g.xanthan gum) and up to 100 wt % water to give a fine active substancesuspension. Dilution with water gives a stable suspension of the activesubstance. For FS type composition up to 40 wt % binder (e.g.polyvinylalcohol) is added.

vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50-80 wt % of the pesticide are ground finely with addition of up to 100wt % dispersants and wetting agents (e.g. sodium lignosulfonate andalcohol ethoxylate) and prepared as water-dispersible or water-solublegranules by means of technical appliances (e. g. extrusion, spray tower,fluidized bed). Dilution with water gives a stable dispersion orsolution of the active substance.

vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

50-80 wt % of the pesticide are ground in a rotor-stator mill withaddition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt %wetting agents (e.g. alcohol ethoxylate) and up to 100 wt % solidcarrier, e.g. silica gel. Dilution with water gives a stable dispersionor solution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt % of the pesticide are comminuted withaddition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt %thickener (e.g. carboxymethylcellulose) and up to 100 wt % water to givea fine suspension of the active substance. Dilution with water gives astable suspension of the active substance.

iv) Microemulsion (ME)

5-20 wt % of the pesticide are added to 5-30 wt % organic solvent blend(e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactantblend (e.g. alcohol ethoxylate and arylphenol ethoxylate), and water upto 100%. This mixture is stirred for 1 h to produce spontaneously athermodynamically stable microemulsion.

iv) Microcapsules (CS)

An oil phase comprising 5-50 wt % of the pesticide, 0-40 wt % waterinsoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt % acrylicmonomers (e.g. methylmethacrylate, methacrylic acid and a di- ortriacrylate) are dispersed into an aqueous solution of a protectivecolloid (e.g. polyvinyl alcohol). Radical polymerization initiated by aradical initiator results in the formation of poly(meth)acrylatemicrocapsules. Alternatively, an oil phase comprising 5-50 wt % of thepesticide, 0-40 wt % water insoluble organic solvent (e.g. aromatichydrocarbon), and an isocyanate monomer (e.g.diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueoussolution of a protective colloid (e.g. polyvinyl alcohol). The additionof a polyamine (e.g. hexamethylenediamine) results in the formation of apolyurea microcapsules. The monomers amount to 1-10 wt %. The wt %relate to the total CS composition.

ix) Dustable Powders (DP, DS)

1-10 wt % of the pesticide are ground finely and mixed intimately withup to 100 wt % solid carrier, e.g. finely divided kaolin.

x) Granules (GR, FG)

0.5-30 wt % of the pesticide is ground finely and associated with up to100 wt % solid carrier (e.g. silicate). Granulation is achieved byextrusion, spray-drying or the fluidized bed.

xi) Ultra-Low Volume Liquids (UL)

1-50 wt % of the pesticide are dissolved in up to 100 wt % organicsolvent, e.g. aromatic hydrocarbon.

The formulation types i) to xi) may optionally comprise furtherauxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt % anti-freezingagents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt % colorants.Preferred composition type is a suspension concentrate.

The agrochemical compositions generally comprise between 0.01 and 95%,preferably between 0.1 and 90%, and most preferably between 0.5 and 75%,by weight of active substance (i.e. pesticide). The active substancesare employed in a purity of from 90% to 100%, preferably from 95% to100% (according to NMR spectrum).

Water-soluble concentrates (LS), Suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. The compositions in question give, aftertwo-to-tenfold dilution, active substance concentrations of from 0.01 to60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-usepreparations. Application can be carried out before or during sowing.Methods for applying or treating the pesticide and compositions thereof,respectively, on to plant propagation material, especially seeds includedressing, coating, pelleting, dusting, soaking and in-furrow applicationmethods of the propagation material. Preferably, the pesticide or thecompositions thereof, respectively, are applied on to the plantpropagation material by a method such that germination is not induced,e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substancesapplied are, depending on the kind of effect desired, from 0.001 to 2 kgper ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. bydusting, coating or drenching seed, amounts of active substance of from0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to100 g and most preferably from 5 to 100 g, per 100 kilogram of plantpropagation material (preferably seed) are generally required.

When used in the protection of materials or stored products, the amountof active substance applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of activesubstance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, ormicronutrients, and other pesticides (e.g. herbicides, insecticides,fungicides, growth regulators, safeners) may be added to the activesubstances or the compositions comprising them as premix or, ifappropriate not until immediately prior to use (tank mix). These agentscan be admixed with the compositions according to the invention in aweight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The concentration of the alkoxylate of the formula (I) in theready-to-use preparation (e.g. the tank mix) is in most cases in therange of from 0.01 to 50 g/I, preferably 0.08 to 10 g/I and inparticular 0.5 to 8 g/I.

The concentration of water in the ready-to-use preparation (e.g. thetank mix) is in most cases at least 60 wt %, preferably at least 75 wt%, and in particular at least 90 wt %.

The user applies the composition according to the invention usually froma predosage device, a knapsack sprayer, a spray tank, a spray plane, oran irrigation system. Usually, the agrochemical composition is made upwith water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, of theready-to-use spray liquor are applied per hectare of agricultural usefularea.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binaryor ternary mixture may be mixed by the user himself in a spray tank andfurther auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the compositionaccording to the invention or partially premixed components, e. g.components comprising the pesticide and the adjuvant, may be mixed bythe user in a spray tank and further auxiliaries and additives may beadded, if appropriate. In a further embodiment, either individualcomponents of the composition according to the invention or partiallypremixed components, e. g. components comprising the pesticide and/orthe adjuvant can be applied jointly (e.g. after tank mix) orconsecutively.

The present invention furthermore relates to a method of preparing thecomposition according to the invention by bringing the adjuvant of theformula (I) and the pesticide into contact, e.g. by mixing. Thecontacting may be done between 5 to 95° C. Thus, a tankmix or aagrochemical composition may be prepared.

The present invention furthermore relates to an alkoxylate of theformula (I) as defined above, where R¹ is a saturated and branched C₁₃alkyl. Mixtures of saturated and branched C₁₃-alkyl are also possible.Further forms or preferred forms of R², R³, R⁴, n, m and AO are asdefined above.

In a form the alkoxylate is of the formula (I) where R¹ is a saturatedand branched C₁₃ alkyl, R² is C₁-C₆ alkyl, R³ and R⁴ are H or C₁-C₄alkyl, AO is ethyleneoxy, or ethyleneoxy and propyleneoxy, n is from 2to 80, and m is from 1 to 3.

In a form the alkoxylate is of the formula (I) where R¹ is a saturatedand branched C₁₃ alkyl, R² is C₄-C₆ alkyl, R³ and R⁴ are H or C₁-C₄alkyl, AO is ethyleneoxy, or ethyleneoxy and propyleneoxy, n is from 2to 80, and m is from 1 to 3.

In a form the alkoxylate is of the formula (I) where R¹ is a saturatedand branched C₁₃ alkyl, R² is C₁-C₆ alkyl, R³ and R⁴ are H or C₁-C₄alkyl, AO is ethyleneoxy, or ethyleneoxy and propyleneoxy, n is from 3to 5, and m is from 1 to 3.

In a form the alkoxylate is of the formula (I) where R¹ is a saturatedand branched C₁₃ alkyl, R² is C₁-C₆ alkyl, R³ and R⁴ are H or C₁-C₄alkyl, AO is ethyleneoxy, or ethyleneoxy and propyleneoxy, n is from 3to 5, and m is from 1 to 3.

In another form the alkoxylate is of the formula (I) where R¹ is asaturated and branched C₁₃ alkyl, R² is n-butyl, R³ and R⁴ are H, AO isethyleneoxy, n is from 2 to 80, and m is from 1 to 3.

In another form the alkoxylate is of the formula (I) where R¹ is asaturated and branched C₁₃ alkyl, R² is n-butyl, R³ and R⁴ are H, AO isethyleneoxy, n is from 2 to 12, and m is from 1 to 2.

The present invention furthermore relates to an alkoxylate of theformula (I) as defined above, where R¹ is 2-propylheptanol. Furtherforms or preferred forms of R², R³, R⁴, n, m and AO are as definedabove.

In a form the alkoxylate is of the formula (I) where R¹ is2-propylheptanol, R² is C₁-C₆ alkyl, R³ and R⁴ are H or C₁-C₄ alkyl, AOis ethyleneoxy, or ethyleneoxy and propyleneoxy, n is from 2 to 80, andm is from 1 to 3.

In another form the alkoxylate is of the formula (I) where R¹ is2-propylheptanol, R² is n-butyl, R³ and R⁴ are H, AO is ethyleneoxy, nis from 2 to 80, and m is from 1 to 3.

In another form the alkoxylate is of the formula (I) where R¹2-propylheptanol, R² is n-butyl, R³ and R⁴ are H, AO is ethyleneoxy, nis from 2 to 12, and m is from 1 to 2.

The present invention furthermore relates to a method of controllingphytopathogenic fungi and/or undesired plant growth and/or undesiredinsect or mite attack and/or for regulating the growth of plants,wherein the composition comprising the pesticide and the alkoxylate ofthe formula (I) according to the invention are allowed to act on therespective pests, their environment or the crop plants to be protectedfrom the respective pest, on the soil and/or on undesired plants and/oron the crop plants and/or on their environment.

The present invention furthermore relates to a method of controllingphytopathogenic fungi and/or undesired plant growth and/or undesiredinsect or mite attack and/or for regulating the growth of plants,wherein a composition comprising a pesticide and the adjuvants of theformula (I) according to the invention (e.g. where R¹ is a saturated andbranched C₁₃ alkyl; or where R¹ is 2-propylheptanol) are allowed to acton the respective pests, their environment or the crop plants to beprotected from the respective pest, on the soil and/or on undesiredplants and/or on the crop plants and/or on their environment.

Examples of suitable crop plants are cereals, for example wheat, rye,barley, triticale, oats or rice; beet, for example sugar or fodder beet;pome fruit, stone fruit and soft fruit, for example apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries, currantsor gooseberries; legumes, for example beans, lentils, peas, lucerne orsoybeans; oil crops, for example oilseed rape, mustard, olives,sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans;cucurbits, for example pumpkins/squash, cucumbers or melons; fibercrops, for example cotton, flax, hemp or jute; citrus fruit, for exampleoranges, lemons, grapefruit or tangerines; vegetable plants, for examplespinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes,potatoes, pumpkin/squash or capsicums; plants of the laurel family, forexample avocados, cinnamon or camphor; energy crops and industrialfeedstock crops, for example maize, soybeans, wheat, oilseed rape, sugarcane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine(dessert grapes and grapes for vinification); hops; grass, for exampleturf; sweetleaf (Stevia rebaudania); rubber plants and forest plants,for example flowers, shrubs, deciduous trees and coniferous trees, andpropagation material, for example seeds, and harvested produce of theseplants.

The term crop plants also includes those plants which have been modifiedby breeding, mutagenesis or recombinant methods, including thebiotechnological agricultural products which are on the market or in theprocess of being developed. Genetically modified plants are plants whosegenetic material has been modified in a manner which does not occurunder natural conditions by hybridizing, mutations or naturalrecombination (i.e. recombination of the genetic material). Here, one ormore genes will, as a rule, be integrated into the genetic material ofthe plant in order to improve the plant's properties. Such recombinantmodifications also comprise posttranslational modifications of proteins,oligo- or polypeptides, for example by means of glycosylation or bindingpolymers such as, for example, prenylated, acetylated or farnesylatedresidues or PEG residues.

The present invention also relates to seed (such as seeds or other plantpropagation materials) comprising the composition according to theinvention. Plant propagation materials can be treated preventively withthe composition according to the invention at the point of or evenbefore sowing or at the point of or even before transplanting. For thetreatment of seed, one will generally use water-soluble concentrates(LS), suspensions (FS), dusts (DS), water-dispersible and water-solublepowders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) andgels (GF). These compositions can be applied to the propagationmaterials, in particular seed, in undiluted form or, preferably, indiluted form. Here, the composition in question can be diluted 2- to10-fold, so that from 0.01 to 60% by weight, preferably from 0.1 to 40%by weight, of active substance is present in the compositions used forthe seed dressing. The application may be effected before or duringsowing. The treatment of plant propagation material, in particular thetreatment of seed, is known to the skilled worker and carried out bydusting, coating, pelleting, dipping or soaking the plant propagationmaterial, the treatment preferably being carried out by pelleting,coating and dusting or by in-furrow treatment so that, for example,untimely early germination of the seed is prevented. It is preferred touse suspensions for the treatment of seed. Usually, such compositionscomprise from 1 to 800 g/l of active substance, from 1 to 200 g/l ofsurfactants, from 0 to 200 g/l of antifreeze agents, from 0 to 400 g/lof binders, from 0 to 200 g/l of colorants and solvent, preferablywater.

The advantages of the invention are high stability of the formulationand of the spray mixture, little wind-caused drift in the case of sprayapplications, good adhesion of the formulation on the surface of thetreated plants, increased solubility of the pesticides in theformulation, increased uptake of the pesticides into the plant, or morerapid or enhanced activity of the pesticide (e.g. even at a low doserate). Other advantages are the high biodegradability of the alkoxylate;the low toxicity of the alkoxylate, the ability of the alkoxylate tolower the surface tension of aqueous compositions, or the increasedspreading on plant surfaces; or the low harmful effect against cropplants, i.e. low phytotoxic effects.

The examples which follow illustrate the invention without imposing anylimitation.

EXAMPLES 1-9 Preparation of Asymmetric Formals

The asymmetric formales were prepared according to known methods.Dibutylglycolformal Bu—O—CH₂—CH₂—O—CH₂—O—CH₂—CH₂—O—Bu was prepared byreacting butylglycol and paraformaldehyde under acidic conditions. Thealkoxylated alcohols R¹-[AO]_(n)—OH according to Table 1 were reactedwith dibutylglycolformal under acidic conditions to yield the asymmetricformals of the formula R¹[O—CH₂—CH₂]_(n)—O—CH₂—O—CH₂—CH₂—O—Bu.

TABLE 1 Example alkoxylated alcohols R¹—[AO]_(n)—OH 1 Ethoxylated (3 EO)C₁₂-C₁₈ fatty alcohol 2 Ethoxylated (5 EO) C₁₂-C₁₈ fatty alcohol 3Ethoxylated (7 EO) C₁₂-C₁₈ fatty alcohol 4 Ethoxylated (3 EO) iso-C₁₃H₂₇alcohol 5 Ethoxylated (5 EO) iso-C₁₃H₂₇ alcohol 6 Ethoxylated (7 EO)iso-C₁₃H₂₇ alcohol 7 Ethoxylated (3 EO) 2-propylhetanol 8 Ethoxylated (4EO) 2-propylhetanol 9 Ethoxylated (5 EO) 2-propylhetanol

EXAMPLE 10 Surface Tension

Physical measurements were done with a solution or dispersion of 1 g/lof the samples from Examples 1-9 in deionized water. The static orequilibrium surface tension is a characteristic value of the interfacialactivity of a formulation in the spray solution. Below the criticalmicelle concentration (CMC) the static surface tension depends on theconcentration of the surface active ingredients in the formulation,whereas above the CMC the static surface tension stays constant. Themeasurement was carried out with the process tensiometer Kruess K 100using the Wilhelmy-Plate-Method. During the measurement the bottom lineof a vertical hanging platinum plate is wetted by the liquid to beanalyzed. The force with which the plate is pulled into the liquid ismeasured and can be converted into the surface tension of the liquid inmN/m. 40 mL of the prepared spray solution are filled into Teflontroughs in the apparatus and the surface tension is detected. The staticsurface tension is calculated once five successive measuring pointsmatch within 0.1 mN/m. The results are summarized in Table 2.

TABLE 2 Sample from Example Surface Tension [mN/m] 1 31 2 30 3 30 4 29 530 6 29 7 29 8 29 9 29

EXAMPLE 11 Increased Biological Activity

The biological activity was assessed in a greenhouse on wheat (species“Kanzler”), which was infected with Puccinia recondita at two leafsstage and incubated for three days at high humidity. The plants weresprayed (spray volume 200 l/ha) with a composition comprising 50 ppm (10g/ha) epoxiconazole and 100 ppm (20 g/ha) of the respective adjuvantsamples from Example 1-9. In the comparative example no adjuvant wasadded. The plants were further cultivated for ten days at 20-24° C. and60-90% relative humidity. Finally, the percentage of the infected leafarea was visually inspected. Each value was based on three replicates.The results are summarized in Table 3.

TABLE 3 Sample from Example Infected leaf area —^(a)) 83 1 7 2 6 3 6 4 85 10 6 12 7 11 8 18 9 12 ^(a))comparative example without adjvuant

EXAMPLE 12 Increased Biological Activity

The biological activity was assessed in a greenhouse as described inExample 11 with a dose rate of 10 g/ha pesticide and 20 g/ha adjuvant(“100%” in Table 4) and a reduced dose rate of 2.5 g/ha pesticide and 5g/ha adjuvant (“25%” in Table 4). The results are summarized in Table 4.In this test the adjuvants from Example 1 (formula A), Example 2(formula B) and as comparative adjuvant butyl endcapped ethoxylated(5EO) n-dodecanol (formula C) were compared. All three compounds arebutyl endcapped. Formula A and C have the same degree of ethoxylation offive ethylene oxide (EO) units. Formula B (only 3 EO) and C have asimilar overall molecule weight.n-C₁₂₋₁₈—[O—CH₂—CH₂]₅—O—CH₂—O—CH₂—CH₂—O—Bu  (A)n-C₁₂₋₁₈—[O—CH₂—CH₂]₃—O—CH₂—O—CH₂—CH₂—O—Bu  (B)n-C₁₂[O—CH₂—CH₂]₅—Bu  (C)

TABLE 4 Infected leaf area Infected leaf area Sample of formula at 100%dose rate at 25% dose rate —^(a),b)) 90 90 (A) 7 23 (B) 6 13 (C)^(a)) 838 ^(a))comparative example. ^(b))without any treatment

EXAMPLE 13 Increased Uptake Rate

Wheat plants (Triticum aestivum variety Melon) were cultivated in thegreenhouse for 6 weeks up to development stage BBCH 39. The plants weretransferred to an automatic lab track sprayer and they were sprayed with125 g/ha epoxiconazole, 125 g/ha fluxapyroxad, and 250 g/ha of therespective adjuvant according to the following parameters:

Water amount: 200 l/ha

Nozzle type: Air injector, ID 120 02 (Lechler, Germany)

Speed: 1.4 m/s

Pressure: 3.33 bar

Subsequently to spraying, the plants were cultivated again in thegreenhouse under ambient conditions. After 8 days samples of 10-15treated leaves were cut off and weighed.

Leaves were cut into small pieces, transferred into glass bottles andwashed with 50% methanol in demineralized water as washing medium for 5min. Then, the washing medium was separated from the leaves. The leaveswere washed again with washing medium for 5 min. Both washing media werecombined and diluted for analysis.

Finally, the leaves were transferred to a vial containing the extractionmedium (75% methanol, 20% water and 5% HCl) and homogenized using aPolytron PT 6100 dispersing unit (Kinematica, CH) for 2 min. 10 ml ofthe extract were centrifuged with 4000 rpm for 5 min. 2 ml of thesupernatant were treated with 2 ml NaOH (0.2 mol/L) and 5 mlcyclohexane, and stirred for 30 min and centrifuged subsequently. 1 mlof the cyclohexane phase was transferred to a glass vial and dried(Liebisch N₂ Evaporator, Germany). The residue was solubilized inmethanol/water 50:50 and analyzed by HPLC-MS/MS.

An Agilent 1100 series HPLC coupled to an Applied Biosystems API 3000triple quadrupole mass spectrometer, equipped with an electro sprayionization source, was used. The mass spectrometer was operated in theMS/MS positive ion mode with multiple reaction monitoring (MRM) usingtwo transitions per analyte at optimized conditions. In addition,unsprayed plants were treated in the same way to see whether they arecontaminated. Unsprayed leaves were spiked with standard activeingredient to determine the recovery of active ingredient during washingand extracting steps. According to the recovery rate the measured samplevalues were corrected.

For comparison a commercially available Berol® 185 from Akzo Nobel wasused, which is an ethoxylated and propoxylated C₁₀-16 alcohol (CAS No69227-22-1), and Adjuvant A, which is an ethoxylated (4EO) andpropoxylated (14 PO) C₁₂₋₁₈ fatty alcohol.

The data showed that the uptake rate of the pesticide was increase whenusing the adjuvants according to the invention compared to Berol® 185 orAdjuvant A.

TABLE 5 Uptake rate Epoxiconazole Fluxapyroxad Sample of Example UptakeRate [%] Uptake Rate [%] —^(a),b)) 8 6 1 45 23 2 40 27 3 40 26 Berol ®185^(a)) 6 4 Adjuvant A^(a)) 28 16 ^(a))comparative example.^(b))without any adjuvant

The invention claimed is:
 1. An agrochemical composition comprising apesticide and an alkoxylate of formula (I)R¹-[AO]_(n)—O—C(R³)(R⁴)—O—[CH₂—CH₂—O]_(m)—R²  (I) where R¹ is a linearor branched, saturated C₁₂-C₂₀ alkyl group, R² is a linear or branched,saturated or unsaturated C₁-C₈ alkyl group, R³ and R⁴ are independentlyfrom one another H or methyl groups, AO is an ethyleneoxy group or amixture of ethyleneoxy and propyleneoxy groups, wherein the unit AO isbound to the unit R¹ via an oxygen atom of the alkyleneoxy group, n isfrom 3 to 10, and m is from 1 to
 3. 2. The composition according toclaim 1, wherein the ratio of n to m is from 10/1 to 1.5/1.
 3. A methodof preparing the composition according to claim 1, by bringing thepesticide and the alkoxylate of the formula (I) into contact.
 4. Amethod of controlling a pest selected from the group consisting ofphytopathogenic fungi and/or undesired plant growth and/or undesiredinsect or mite attack and/or for regulating the growth of plants,wherein the agrochemical composition comprising the pesticide and thealkoxylate of the formula (I) as defined in claim 1 are allowed to acton the respective pests, their environment or the crop plants to beprotected from the respective pest, on the soil and/or on undesiredplants and/or on the crop plants and/or on their environment.
 5. A seedtreated with the agrochemical composition as defined in claim
 1. 6. Themethod of claim 4, wherein the ratio of n to m is from 10/1 to 1.5/1. 7.The composition according to claim 1, wherein m is from 1 to
 2. 8. Thecomposition according to claim 7, wherein AO is ethyleneoxy.
 9. Thecomposition according to claim 1, wherein: m is from 1 to 2; AO isethyleneoxy; R¹ is a linear or branched, saturated C₁₂-C₁₈ alkyl group,R² is a linear or branched, saturated C₂-C₄ alkyl group R³ and R⁴ areindependently from one another H, and the ratio of n to m is from 9/1 to2/1.